DE10129970A1 - Coating materials curable thermally and with actinic radiation, process for their preparation and their use - Google Patents

Abstract

The invention relates to coating materials which can be cured thermally and by means of actinic radiation, comprising: (A) at least one binding agent containing isocyanate-reactive functional groups and (B) a cross-linking agent component containing (i) free and/or blocked isocyanate groups, (ii) reactive functional groups containing at least one bond which can be activated by actinic radiation, (iii) flexible segments which, as a constituent of three-dimensional networks, lower their glass transition temperature Tg, and (iv) curing segments which, as a constituent of three-dimensional networks, increase their glass transition temperature Tg, provided that the cross-linking agent component (B) comprises at least one constituent having the characteristics (i) and (ii) or consists thereof. The invention also relates to a method for producing said coating materials and the use thereof.

Description

The present invention relates to new, thermal and with actinic radiation curable coating materials. The present invention also relates to a new process for the production of heat and curable with actinic radiation Coating materials. The present invention further relates to Use of the new, curable thermally and with actinic radiation Coating materials in the field of automotive OEM painting, the Automotive refinishing, the coating of buildings in the interior and Exterior, painting furniture, windows or doors and the industrial painting, including coil coating, container coating, the Impregnation or coating of electrical components and the Coating of white goods, including household appliances, boilers and Radiators.

In the context of the present invention is under actinic radiation electromagnetic radiation such as near infrared (NIR), visible light, UV Radiation and x-rays or corpuscular radiation like To understand electron radiation.

Coating materials, adhesives and sealants that are both thermal and are also curable with actinic radiation (dual-cure coating materials, Adhesives and sealants) are gaining more and more interest because of them offer numerous advantages.

For example, dual-cure coating materials are better for coating thermally sensitive substrates suitable as coating materials that only are thermally curable as they may be incomplete thermal curing at low temperatures by curing with actinic Radiation can be compensated for, so that overall coatings with good application properties result. Second, dual-cure Coating materials better for coating complex shaped three-dimensional substrates suitable as coating materials that only with actinic radiation are curable, because incomplete radiation curing in the Shadow areas of the substrates are compensated by the thermal curing can be, so that here too overall coatings with good application properties result.

This also applies mutatis mutandis to the dual-cure adhesives and Sealing compounds.

Dual-cure coating materials are from the German patent application DE 198 18 735 A1 known. The dual-cure coating materials contain components such as B. (meth) acrylate copolymers which are functional in addition to isocyanate-reactive Groups have mandatory (meth) acryloyl groups, and components such as z. B. (meth) acrylate copolymers, in addition to complementary free Isocyanate groups also have mandatory (meth) acryloyl groups. They can also contain thermally curable components such as Contain (meth) acrylate copolymers which are free of (meth) acryloyl groups, meanwhile have isocyanate-reactive groups. In addition, the German patent application a variety of alternatives to these Components that are all represented as having the same effect.

It is stated that the known dual-cure coating materials Coatings with very good chemical, petrol and solvent resistance, result in high scratch resistance and good and rapid sandability and in this Regarding the requirements for a multi-layer coating in the field of Vehicle painting, especially vehicle refinishing, is sufficient should. In addition, the coatings should be free of cracks and have good adhesion to the surface. Overall, they should be one show perfect optical appearance. However, like this property profile can be set and optimized in detail and which of the practical best of countless alternatives that can be derived from several lists will work, neither in the description nor with an example concretized.

European patent application EP 0 928 800 A1 describes a dual-cure Coating material known to contain a urethane (meth) acrylate with free Isocyanate groups and (meth) acryloyl groups, a photoinitiator and one Isocyanate-reactive compound, in particular a polyol or polyamine. Specifically, a urethane (meth) acrylate based on a trimer of Hexamethylene diisocyanate described.

The previously known dual-cure coating materials provide coatings that have a high scratch resistance. Your etch resistance, i.e. H. your Resistance to acid rain, its weather resistance and Chemical resistance still leaves something to be desired. You meet usual and known measures to improve these properties will Reduced scratch resistance of the coatings.

• A) ein Bindemittel, das frei ist von Kohlenstoff-Kohlenstoff-Doppelbindungen, die mit aktinischer Strahlung aktivierbar sind, enthaltend mindestens ein (Meth)Acrylatcopolymerisat mit im statistischen Mittel mindestens einer isocyanatreaktiven funktionellen Gruppe und mindestens einer Ionen bildenden Gruppe im Molekül,
• B) mindestens ein blockiertes und/oder teilblockiertes Polyisocyanat und
• C) mindestens einen olefinisch ungesättigten Bestandteil, der frei ist von isocyanatreaktiven funktionellen Gruppen und im statistischen Mittel mehr als vier mit aktinischer Strahlung aktivierbare Kohlenstoff-Kohlenstoff- Doppelbindungen im Molekül enthält.

The unpublished German patent application DE 101 15 605.7 describes powder slurries which are curable thermally and with actinic radiation and which contain solid and / or highly viscous particles which are dimensionally stable under storage and use conditions. The dimensionally stable particles contain

• A) a binder which is free from carbon-carbon double bonds which can be activated with actinic radiation, comprising at least one (meth) acrylate copolymer with on average at least one isocyanate-reactive functional group and at least one ion-forming group in the molecule,
• B) at least one blocked and / or partially blocked polyisocyanate and
• C) at least one olefinically unsaturated constituent which is free from isocyanate-reactive functional groups and, on a statistical average, contains more than four carbon-carbon double bonds in the molecule which can be activated with actinic radiation.

Polyisocyanates (B) which contain at least one flexible segment that is part of three-dimensional networks Glass transition temperature Tg lowered, contained in the molecule.

Preferably, olefinically unsaturated component (C) are used, which at least one hardening segment that is part of three-dimensional Networks whose glass transition temperature Tg increases, contained in the molecule.

The object of the present invention is to create new ones thermally and with actinic ones Radiation curable coating materials provide the coatings deliver that, in addition to high scratch resistance, also a high etching Resistance, chemical resistance and weather resistance. The new, curable thermally and with actinic radiation Coating materials to be easy to manufacture and apply. Moreover the new, thermally and with actinic radiation curable Coating materials can be used widely.

• A) mindestens ein Bindemittel mit isocyanatreaktiven funktionellen Gruppen und
• B) eine Vernetzungsmittelkomponente, enthaltend
  • a) freie und/oder blockierte Isocyanatgruppen,
  • b) reaktive funktionelle Gruppen, enthaltend mindestens eine mit aktinischer Strahlung aktivierbare Bindung,
  • c) flexibilisierende Segmente, die als Bestandteil dreidimensionaler Netzwerke deren Glasübergangstemperatur Tg erniedrigen, und
  • d) hartmachende Segmente, die als Bestandteil dreidimensionaler Netzwerke deren Glasübergangstemperatur Tg erhöhen;
  mit der Maßgabe, daß die Vernetzungsmittelkomponente (B) mindestens einen Bestandteil enthält, der die Merkmale (i) und (ii) aufweist.

Accordingly, the new coating materials curable thermally and with actinic radiation have been found to contain

• A) at least one binder with isocyanate-reactive functional groups and
• B) containing a crosslinking agent component
  • a) free and / or blocked isocyanate groups,
  • b) reactive functional groups containing at least one bond which can be activated with actinic radiation,
  • c) flexibilizing segments which, as a component of three-dimensional networks, lower their glass transition temperature Tg, and
  • d) hardening segments which, as a component of three-dimensional networks, increase their glass transition temperature Tg;
  with the proviso that the crosslinking agent component (B) contains at least one component which has the features (i) and (ii).

The following are the new ones, thermal and with actinic radiation curable coating materials as "coating materials according to the invention" designated.

Further objects of the invention result from the description.

In view of the prior art, it was surprising and for the One skilled in the art could not have foreseen that the object of the present invention was based, can be solved with the help of the coating materials of the invention could. It was particularly surprising that the use of the Crosslinking agent component (B) in the coatings according to the invention the scissors closed between the etch resistance and the scratch resistance could be. The broad applicability of the coating materials according to the invention, also as adhesives and Sealing compounds used for the production of adhesive layers and seals could become.

The first essential component of the coating materials according to the invention is at least one binder (A) with on average at least one, preferably at least two and in particular at least three isocyanate-reactive functional group (s) in the molecule.

Examples of suitable isocyanate-reactive functional groups are hydroxyl, Thiol and primary and secondary amino groups, in particular Hydroxyl groups.

The binder (A) can also at least one, in particular at least two of the reactive functional described below Groups with at least one bond that can be activated with actinic radiation contain.

Examples of suitable binders (A) are thermal or thermal and with actinic radiation curable, statistical, alternating and / or block-like constructed linear and / or branched and / or comb-like (Co) polymers of ethylenically unsaturated monomers, polyaddition resins and / or polycondensation resins. These terms are supplemented by Römpp Lexicon Lacke und Druckfarben, Georg Thieme Verlag, Stuttgart, New York, 1998, page 457, "polyaddition" and "polyaddition resins (polyadducts)", and pages 463 and 464, "Polycondensates", "Polycondensation" and "Polycondensation resins", as well as pages 73 and 74, "Binder".

Examples of suitable (co) polymers (A) are (meth) acrylate (co) polymers or partially saponified polyvinyl esters, in particular (meth) acrylate copolymers.

Examples of suitable polyaddition resins and / or polycondensation resins (A) are polyesters, alkyds, polyurethanes, polylactones, polycarbonates, polyethers, Epoxy-amine adducts, polyureas, polyamides, polyimides, polyester Polyurethanes, polyether-polyurethanes or polyester-polyether-polyurethanes, especially polyester.

Of these binders (A), the (meth) acrylate copolymers and Polyester have particular advantages and are therefore particularly preferred used.

• 1. Monomere, welche mindestens eine Hydroxyl- oder Aminogruppe pro Molekül tragen, wie
  • - Hydroxyalkylester der Acrylsäure, Methacrylsäure oder einer anderen alpha,beta-olefinisch ungesättigten Carbonsäure, die sich von einem Alkylenglykol ableiten, das mit der Säure verestert ist, oder die durch Umsetzung der alpha,beta-olefinisch ungesättigten Carbonsäure mit einem Alkylenoxid wie Ethylenoxid oder Propylenoxid erhältlich sind, insbesondere Hydroxyalkylester der Acrylsäure, Methacrylsäure, Ethacrylsäure, Crotonsäure, Maleinsäure, Fumarsäure oder Itaconsäure, in denen die Hydroxyalkylgruppe bis zu 20 Kohlenstoffatome enthält, wie 2- Hydroxyethyl-, 2-Hydroxypropyl-, 3-Hydroxypropyl-, 3-Hydroxybutyl-, 4-Hydroxybutylacrylat, -methacrylat, -ethacrylat, -crotonat, -maleinat, -fumarat oder -itaconat; oder Hydroxycycloalkylester wie 1,4- Bis(hydroxymethyl)cyclohexan-, Octahydro-4,7-methano-1H-indendimethanol- oder Methylpropandiolmonoacrylat, -monomethacrylat, -monoethacrylat, -monocrotonat, -monomaleinat, -monofumarat oder -monoitaconat; Umsetzungsprodukte aus cyclischen Estern, wie z. B. epsilon-Caprolacton und diesen Hydroxyalkyl- oder -cycloalkylestern;
  • - olefinisch ungesättigte Alkohole wie Allylalkohol;
  • - Polyole wie Trimethylolpropanmono- oder diallylether oder Pentaerythritmono-, -di- oder -triallylether;
  • - Umsetzungsprodukte aus Acrylsäure und/oder Methacrylsäure mit dem Glycidylester einer in alpha-Stellung verzweigten Monocarbonsäure mit 5 bis 18 C-Atomen je Molekül, insbesondere einer Versatic®-Säure, oder anstelle des Umsetzungsproduktes eine äquivalenten Menge Acryl- und/oder Methacrylsäure, die dann während oder nach der Polymerisationsreaktion mit dem Glycidylester einer in alpha-Stellung verzweigten Monocarbonsäure mit 5 bis 18 C-Atomen je Molekül, insbesondere einer Versatic®-Säure, umgesetzt wird;
  • - Aminoethylacrylat, Aminoethylmethacrylat, Allylamin oder N- Methyliminoethylacrylat; und/oder
  • - Acryloxysilan-enthaltende Vinylmonomere, herstellbar durch Umsetzung hydroxyfunktioneller Silane mit Epichlorhydrin und anschließender Umsetzung des Reaktionsproduktes mit (Meth)acrylsäure und/oder Hydroxyalkyl- und/oder -cycloalkylestern der (Meth)Acrylsäure und/oder weiterer hydroxylgruppehaltiger Monomere (a1).
• 2. Monomere, welche mindestens eine Säuregruppe pro Molekül tragen, wie
  • - Acrylsäure, beta-Carboxyethylacrylat, Methacrylsäure, Ethacrylsäure, Crotonsäure, Maleinsäure, Fumarsäure oder Itaconsäure;
  • - olefinisch ungesättigte Sulfon- oder Phosphonsäuren oder deren Teilester;
  • - Maleinsäuremono(meth)acryloyloxyethylester, Bernsteinsäuremono(meth)acryloyloxyethylester oder Phthalsäuremono(meth)acryloyloxyethylester; oder
  • - Vinylbenzoesäure (alle Isomere), alpha-Methylvinylbenzoesäure (alle Isomere) oder Vinylbenzsolsulfonsäure (alle Isomere).
• 3. Monomere, die im wesentlichen oder völlig frei von reaktiven funktionellen Gruppen sind, wie:

Examples of suitable olefinically unsaturated monomers (a) for the preparation of the (meth) acrylate copolymers (A) are

• 1. Monomers which carry at least one hydroxyl or amino group per molecule, such as
  • - Hydroxyalkyl esters of acrylic acid, methacrylic acid or another alpha, beta-olefinically unsaturated carboxylic acid derived from an alkylene glycol esterified with the acid, or by reacting the alpha, beta-olefinically unsaturated carboxylic acid with an alkylene oxide such as ethylene oxide or propylene oxide are available, in particular hydroxyalkyl esters of acrylic acid, methacrylic acid, ethacrylic acid, crotonic acid, maleic acid, fumaric acid or itaconic acid, in which the hydroxyalkyl group contains up to 20 carbon atoms, such as 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 3-hydroxybutyl , 4-hydroxybutyl acrylate, methacrylate, ethacrylate, crotonate, maleate, fumarate or itaconate; or hydroxycycloalkyl esters such as 1,4-bis (hydroxymethyl) cyclohexane, octahydro-4,7-methano-1H-indendimethanol or methyl propanediol monoacrylate, monomethacrylate, monoethacrylate, monocrotonate, monomaleinate, monofumarate or monoitaconate; Reaction products from cyclic esters, such as. B. epsilon-caprolactone and these hydroxyalkyl or cycloalkyl esters;
  • - olefinically unsaturated alcohols such as allyl alcohol;
  • - Polyols such as trimethylolpropane mono- or diallyl ether or pentaerythritol mono-, di- or triallyl ether;
  • - Reaction products from acrylic acid and / or methacrylic acid with the glycidyl ester of a monocarboxylic acid with 5 to 18 carbon atoms per molecule branched in the alpha position, in particular one Versatic® acid, or instead of the reaction product, an equivalent amount of acrylic and / or methacrylic acid, which then during or after the polymerization reaction with the glycidyl ester of a monocarboxylic acid branched in the alpha position with 5 to 18 carbon atoms per molecule, in particular a Versatic® acid, is reacted;
  • - aminoethyl acrylate, aminoethyl methacrylate, allylamine or N-methyliminoethyl acrylate; and or
  • - Acryloxysilane-containing vinyl monomers, which can be prepared by reacting hydroxy-functional silanes with epichlorohydrin and then reacting the reaction product with (meth) acrylic acid and / or hydroxyalkyl and / or cycloalkyl esters of (meth) acrylic acid and / or other hydroxyl-containing monomers (a1).
• 2. Monomers which carry at least one acid group per molecule, such as
  • - Acrylic acid, beta-carboxyethyl acrylate, methacrylic acid, ethacrylic acid, crotonic acid, maleic acid, fumaric acid or itaconic acid;
  • - Olefinically unsaturated sulfonic or phosphonic acids or their partial esters;
  • - Maleic acid mono (meth) acryloyloxyethyl ester, succinic acid mono (meth) acryloyloxyethyl ester or phthalic acid mono (meth) acryloyloxyethyl ester; or
  • - vinylbenzoic acid (all isomers), alpha-methylvinylbenzoic acid (all isomers) or vinylbenzenesulfonic acid (all isomers).
• 3. Monomers that are essentially or completely free of reactive functional groups, such as:

Monomers (a31)

Essentially acid group-free (meth) acrylic acid esters such as (Meth) acrylic acid alkyl or cycloalkyl esters with up to 20 Carbon atoms in the alkyl radical, in particular methyl, ethyl, n-propyl, n- Butyl, sec-butyl, tert-butyl, hexyl, ethylhexyl, stearyl and Lauryl acrylate or methacrylate; cycloaliphatic (meth) acrylic acid esters, especially cyclohexyl, isobornyl, dicyclopentadienyl, octahydro-4,7- methano-1H-indene methanol or tert-butylcyclohexyl (meth) acrylate; (Meth) acrylic acid oxaalkyl esters or oxacycloalkyl esters such as Ethoxytriglycol (meth) acrylate and methoxyoligoglycol (meth) acrylate with one Molecular weight Mn of preferably 550 or other ethoxylated and / or propoxylated (meth) acrylic acid derivatives free of hydroxyl groups (Further examples of suitable monomers (31) of this type are from the Laid-open specification DE 196 25 773 A1, column 3, line 65, to column 4, Line 20, known). These can be in minor quantities higher functional (meth) acrylic acid alkyl or cycloalkyl esters such as Ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, Butylene glycol, pentane-1,5-diol, hexane-1,6-diol, octahydro-4,7-methano- 1H-indendimethanol- or cyclohexane-1,2-, -1,3- or -1,4-diol di (meth) acrylate; Trimethylolpropane di- or tri (meth) acrylate; or Contain pentaerythritol di-, tri- or tetra (meth) acrylate. Framework of the The present invention are in subordinate amounts higher functional monomers (a31) to understand such amounts which do not lead to crosslinking or gelling of the copolymers, be it because they should be in the form of cross-linked microgel particles.

Monomers a32

Vinyl esters of monocarboxylic acids branched in the alpha position with 5 to 18 carbon atoms in the molecule. The branched monocarboxylic acids can are obtained by reacting formic acid or carbon monoxide and water with olefins in the presence of a liquid, strongly acidic catalyst; The olefins can be paraffinic crack products Hydrocarbons, such as mineral oil fractions, can and can be both branched and straight-chain acyclic and / or cycloaliphatic olefins contain. In the implementation of such olefins with formic acid or with Carbon monoxide and water form a mixture of carboxylic acids which the carboxyl groups predominantly on a quaternary Carbon atom sit. Other olefinic starting materials are e.g. B. Propylene trimer, propylene tetramer and diisobutylene. The vinyl esters can but can also be prepared from the acids in a manner known per se, z. B. by allowing the acid to react with acetylene. Especially because of the good availability, vinyl esters from saturated aliphatic monocarboxylic acids with 9 to 11 carbon atoms, the are branched on the alpha-C atom. Vinyl esters of this type sold under the VeoVa® brand (see also Römpp Lexikon Lacke and Printing colors, Georg Thieme Verlag, Stuttgart, New York, 1998, page 598).

Monomers (a33)

Diarylethylenes, in particular those of the general formula I:

R ¹ R ² C = CR ³ R ⁴ (I),

wherein the radicals R ¹ , R ² , R ³ and R ⁴ each independently represent hydrogen atoms or substituted or unsubstituted alkyl, cycloalkyl, alkylcycloalkyl, cycloalkylalkyl, aryl, alkylaryl, cycloalkylaryl, arylalkyl or arylcycloalkyl radicals provided that at least two of the variables R ¹ , R ² , R ³ and R ^{4 represent} substituted or unsubstituted aryl, arylalkyl or arylcycloalkyl radicals, in particular substituted or unsubstituted aryl radicals. Examples of suitable alkyl radicals are methyl, ethyl, propyl, isopropyl, n-butyl, iso-butyl, tert-butyl, amyl, hexyl or 2-ethylhexyl. Examples of suitable cycloalkyl radicals are cyclobutyl, cyclopentyl or cyclohexyl. Examples of suitable alkylcycloalkyl radicals are methylenecyclohexane, ethylenecyclohexane or propane-1,3-diylcyclohexane. Examples of suitable cycloalkylalkyl radicals are 2-, 3- or 4-methyl, ethyl, propyl or butylcyclohex-1-yl. Examples of suitable aryl radicals are phenyl, naphthyl or biphenylyl, preferably phenyl and naphthyl and in particular phenyl. Examples of suitable alkylaryl radicals are benzyl or ethylene or propane-1,3-diyl-benzene. Examples of suitable cycloalkylaryl radicals are 2-, 3- or 4-phenylcyclohex-1-yl. Examples of suitable arylalkyl radicals are 2-, 3- or 4-methyl-, ethyl-, propyl- or butylphen-1-yl. Examples of suitable arylcycloalkyl radicals are 2-, 3- or 4-cyclohexylphen-1-yl. The aryl radicals R ¹ , R ² , R ³ and / or R ⁴ are preferably phenyl or naphthyl radicals, in particular phenyl radicals. The substituents optionally present in the radicals R ¹ , R ² , R ³ and / or R ⁴ are electron-withdrawing or electron-donating atoms or organic radicals, in particular halogen atoms, nitrile, nitro, partially or completely halogenated alkyl, cycloalkyl, alkylcycloalkyl , Cycloalkylalkyl, aryl, alkylaryl, cycloalkylaryl, arylalkyl and arylcycloalkyl radicals; Aryloxy, alkyloxy and cycloalkyloxy radicals; and / or arylthio, alkylthio and cycloalkylthio radicals. Diphenylethylene, dinaphthaleneethylene, cis- or trans-stilbene or vinylidene-bis (4-nitrobenzene), in particular diphenylethylene (DPE), are particularly advantageous, which is why they are preferably used. In the context of the present invention, the monomers (b33) are used in order to regulate the copolymerization advantageously in such a way that a free-radical copolymerization in batch mode is also possible.

Monomers (a34)

Vinyl aromatic hydrocarbons such as styrene, vinyl toluene, Diphenylethylene or alpha-alkylstyrenes, especially alpha-methylstyrene.

Monomers (a35)

Nitriles such as acrylonitrile and / or methacrylonitrile.

Monomers a36

Vinyl compounds, especially vinyl and / or vinylidene dihalides such as Vinyl chloride, vinyl fluoride, vinylidene dichloride or vinylidene difluoride; N- Vinyl amides such as vinyl-N-methylformamide, N-vinylcaprolactam or N- vinylpyrrolidone; 1-vinylimidazole; Vinyl ethers such as ethyl vinyl ether, n- Propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether and / or vinylcyclohexyl ether; and / or vinyl esters such as vinyl acetate, Vinyl propionate, vinyl butyrate, vinyl pivalate and / or the vinyl ester of 2- Methyl-2-ethylheptanoic acid.

Monomers a37

Allyl compounds, especially allyl ethers and esters such as allylmethyl, ethyl, propyl or butyl ether or allyl acetate, propionate or butyrate.

Monomers (a38)

Polysiloxane macromonomers which have a number average molecular weight Mn from 1,000 to 40,000 and on average 0.5 to 2.5 ethylenically unsaturated Have double bonds per molecule; in particular Polysiloxane macromonomers which have a number average molecular weight Mn from 2,000 to 20,000, particularly preferably 2,500 to 10,000 and in particular 3,000 to 7,000 and on average 0.5 to 2.5, preferably 0.5 to 1.5, ethylenically unsaturated double bonds per molecule, such as see DE 38 07 571 A1 on pages 5 to 7, DE 37 06 095 A1 in columns 3 to 7 of EP 0 358 153 B1 on pages 3 to 6, in the US 4,754,014 A1 in columns 5 to 9, in DE 44 21 823 A1 or in international patent application WO 92/22615 on page 12, line 18, to Page 18, line 10.

Monomers (a39)

• 1. Epoxidgruppen enthaltende Monomere wie der Glycidylester der Acrylsäure, Methacrylsäure, Ethacrylsäure, Crotonsäure, Maleinsäure, Fumarsäure oder Itaconsäure oder Allylglycidylether.

Olefins such as ethylene, propylene, but-1-ene, pent-1-ene, hex-1-ene, cyclohexene, cyclopentene, norbornene, butadiene, isoprene, cyclopentadiene and / or dicyclopentadiene.
and or

• 1. Monomers containing epoxy groups, such as the glycidyl ester of acrylic acid, methacrylic acid, ethacrylic acid, crotonic acid, maleic acid, fumaric acid or itaconic acid or allyl glycidyl ether.

Higher functional monomers of the type described above are in generally used in minor amounts. As part of the present Invention are subordinate amounts of higher functional monomers to understand such amounts that are not necessary for crosslinking or gelling the (Meth) acrylate copolymers (A) lead, unless you want to crosslink produce polymeric microparticles.

The (meth) acrylate copolymers (A) have, depending on the intended use coating material according to the invention a glass transition temperature of -50 ° C. to +110, preferably -30 to +80, preferably -15 to +70, particularly preferably -15 to +50, very particularly preferably -15 to +40 and in particular -15 to + 30 ° C. Their acid number depends primarily on whether they are in aqueous coating materials according to the invention are to be used; the acid number is preferably 5 to 100 mg KOH / g. Likewise, their salary vary widely on isocyanate-reactive groups, especially hydroxyl groups; preferably their hydroxyl number is 20 to 300, preferably 30 to 250, particularly preferably 40 to 200, very particularly preferably 60 to 190 in particular 80 to 180 mg KOH / g. Particular advantages result from the Use of the monomers (a2) 2-hydroxypropyl, 3-hydroxypropyl, 3- Hydroxybutyl and 4-hydroxybutyl acrylate and methacrylate.

Examples of suitable production processes for (meth) acrylate copolymers (A) are in European patent applications EP 0 767 185 A1, the German Patents DE 22 14 650 B1 or DE 27 49 576 B1 and the American Patents US 4,091,048 A1, US 3,781,379 A1, US 5,480,493 A1, US 5,475,073 A1 or US 5,534,598 A1 or in the standard work Houben-Weyl, Methods of organic chemistry, 4th edition, volume 14 / l, pages 24 to 255, 1961. The usual reactors for the copolymerization are and known stirred tanks, stirred tank cascades, tubular reactors, Loop reactors or Taylor reactors, such as those in the Patent specifications and patent applications DE 10 71 241 B1, EP 0 498 583 A1 or DE 198 28 742 A1 or in the article by K. Kataoka in Chemical Engineering Science, volume 50, number 9, 1995, pages 1409 to 1416 be considered.

Examples of suitable polyesters are in particular aliphatic polyesters on the Base of hexahydrophthalic anhydride. The polyesters are commercially available Products and are sold, for example, under the Desmophen® 2089, A 575 brand and 670 distributed by Bayer AG.

The production of such polyesters is, for example, in the standard work Ullmann's Encyclopedia of Technical Chemistry, 3rd Edition, Volume 14, Urban & Schwarzenberg, Munich, Berlin, 1963, pages 80 to 89 and pages 99 to 105, and in the books: "Resines Alkydes-Polyesters" by J. Bourry, Paris, Verlag Dunod, 1952, "Alkyd Resins" by C. R. Martens, Reinhold Publishing Corporation, New York, 1961, and "Alkyd Resin Technology" by T.C. Patton, Intersience Publishers, 1962.

The introduction of reactive functional groups with at least one through Actinic radiation can be activated by binding polymer-analogous implementation of those described above (Meth) acrylate copolymers (A) with suitable compounds through contain actinic bonds that can be activated. For example can optionally existing side glycidyl groups of (Meth) acrylate copolymers (A) are reacted with (meth) acrylic acid. Or it some of the hydroxyl groups can be reacted with compounds which a free isocyanate group and at least one, especially one, with contain bond that can be activated by actinic radiation. Examples of suitable ones Compounds of this type are 1- (1-isocyanato-1-methylethyl) -3- (1-methylethenyl) - benzene (TMI® from Cytec) or vinyl isocyanate.

The content of the coating materials according to the invention in the binders (A) can vary widely and depends primarily on the functionality of the Binder (A) on the one hand and crosslinking agent (B) on the other. The content, based on the solid, is preferably one coating material according to the invention, at 20 to 90, preferably 25 to 85, particularly preferably 30 to 80, very particularly preferably 35 to 75 and in particular 40 to 70 wt .-%.

The further essential component of the coating materials according to the invention is the crosslinking agent component (B).

• a) freie und/oder blockierte Isocyanatgruppen,
• b) reaktive funktionelle Gruppen, enthaltend mindestens eine mit aktinischer Strahlung aktivierbare Bindung,
• c) flexibilisierende Segmente, die als Bestandteil dreidimensionaler Netzwerke deren Glasübergangstemperatur Tg erniedrigen, und
• d) hartmachende Segmente, die als Bestandteil dreidimensionaler Netzwerke deren Glasübergangstemperatur Tg erhöhen,

enthält, mit der Maßgabe, daß die Vernetzungsmittelkomponente (B) mindestens einen Bestandteil enthält, der die Merkmale (i) und (ii) aufweist. The crosslinking agent component (B) to be used according to the invention can have any composition, as long as it only

• a) free and / or blocked isocyanate groups,
• b) reactive functional groups containing at least one bond which can be activated with actinic radiation,
• c) flexibilizing segments which, as a component of three-dimensional networks, lower their glass transition temperature Tg, and
• d) hardening segments which, as a component of three-dimensional networks, increase their glass transition temperature Tg,

contains, with the proviso that the crosslinking agent component (B) contains at least one component which has the features (i) and (ii).

In addition, the crosslinking agent component (B) can also be conventional and known polyisocyanates that have no reactive functional groups have at least one bond that can be activated with actinic radiation, contain.

• 1. mindestens einen, insbesondere einen, Bestandteil, enthaltend im Molekül im statistischen Mittel
  • a) mindestens eine, insbesondere mindestens zwei, freie und/oder mindestens eine, insbesondere mindestens zwei, blockierte Isocyanatgruppe(n),
  • b) mindestens eine, insbesondere mindestens zwei, reaktive funktionelle Gruppe(n) mit mindestens einer, insbesondere einer, mit aktinischer Strahlung aktivierbaren Bindung und
  • c) mindestens ein flexibilisierendes Segment, vorzugsweise mindestens zwei und insbesondere mindestens drei flexibilisierende Segmente, die als Bestandteil dreidimensionaler Netzwerke deren Glasübergangstemperatur Tg erniedrigen; und
• 2. mindestens einen, insbesondere einen, Bestandteil, enthaltend im Molekül im statistischen Mittel
  • a) mindestens eine, insbesondere mindestens zwei, freie und/oder mindestens eine, insbesondere mindestens zwei, blockierte Isocyanatgruppe(n),
  • b) mindestens eine, insbesondere mindestens zwei, reaktive funktionelle Gruppe(n) mit mindestens einer, insbesondere einer, mit aktinischer Strahlung aktivierbaren Bindung und
  • c) mindestens ein hartmachendes Segment, vorzugsweise mindestens zwei und insbesondere mindestens drei hartmachende Segmente die als Bestandteil dreidimensionaler Netzwerke deren Glasübergangstemperatur Tg erhöhen;

oder es besteht hieraus. Demgemäß werden bei dieser bevorzugten Ausführungsform die beiden Bestandteil oder Vernetzungsmittel (B1) und (B2) getrennt voneinander hergestellt und erst bei der Herstellung des erfindungsgemäßen Beschichtungsstoffs zu der Vernetzungsmittelkomponente (B) vereinigt. In a first preferred embodiment, the crosslinking agent component (B) contains

• 1. at least one, in particular one, constituent containing in the molecule on average
  • a) at least one, in particular at least two, free and / or at least one, in particular at least two, blocked isocyanate group (s),
  • b) at least one, in particular at least two, reactive functional group (s) with at least one, in particular one, bond which can be activated with actinic radiation and
  • c) at least one flexibilizing segment, preferably at least two and in particular at least three flexibilizing segments, which lower the glass transition temperature Tg as part of three-dimensional networks; and
• 2. at least one, in particular one, constituent contained in the molecule on average
  • a) at least one, in particular at least two, free and / or at least one, in particular at least two, blocked isocyanate group (s),
  • b) at least one, in particular at least two, reactive functional group (s) with at least one, in particular one, bond which can be activated with actinic radiation and
  • c) at least one hardening segment, preferably at least two and in particular at least three hardening segments, which increase the glass transition temperature Tg as a component of three-dimensional networks;

or it consists of it. Accordingly, in this preferred embodiment, the two constituents or crosslinking agents (B1) and (B2) are prepared separately from one another and are only combined to form the crosslinking agent component (B) when the coating material according to the invention is produced.

• 1. eines Gemischs aus
  • 1. 1.1) mindestens einem, insbesondere einem, Polyisocyanat, enthaltend im Molekül im statistischen Mittel mindestens zwei, insbesondere mindestens drei, freie Isocyanatgruppen, oder mindestens zwei, insbesondere mindestens drei, freie und mindestens eine, insbesondere mindestens zwei, blockierte Isocyanatgruppe(n) sowie mindestens ein flexibilisierendes Segment, vorzugsweise mindestens zwei und insbesondere mindestens drei flexibilisierende Segmente, die als Bestandteil dreidimensionaler Netzwerke deren Glasübergangstemperatur Tg erniedrigen; und
  • 2. 1.2) mindestens einem, insbesondere einem, Polyisocyanat, enthaltend im Molekül im statistischen Mittel mindestens zwei, insbesondere mindestens drei, freie Isocyanatgruppen, oder mindestens zwei, insbesondere mindestens drei, freie und mindestens eine, insbesondere mindestens zwei, blockierte Isocyanatgruppe sowie mindestens ein hartmachendes Segment, vorzugsweise mindestens zwei und insbesondere mindestens drei hartmachende Segmente, die als Bestandteil dreidimensionaler Netzwerke deren Glasübergangstemperatur Tg erhöhen; mit
• 2. mindestens einer, insbesondere einer, Verbindung, enthaltend im Molekül im statistischen Mittel mindestens eine, insbesondere eine, isocyanatreaktive funktionelle Gruppe und mindestens eine, insbesondere eine, reaktive funktionelle Gruppe mit mindestens einer mit aktinischer Strahlung aktivierbaren Bindung;

oder sie besteht aus diesen Bestandteilen. According to a further preferred embodiment, the crosslinking agent component (B) contains at least two constituents which can be prepared by the one- or multi-stage, in particular one-stage, reaction

• 1. a mixture of
  • 1. 1.1) at least one, in particular one, polyisocyanate containing, on average, at least two, in particular at least three, free isocyanate groups in the molecule, or at least two, in particular at least three, free and at least one, in particular at least two, blocked isocyanate group (s) as well as at least one flexibilizing segment, preferably at least two and in particular at least three flexibilizing segments, which lower the glass transition temperature Tg as a component of three-dimensional networks; and
  • 2. 1.2) at least one, in particular one, polyisocyanate containing in the molecule on average at least two, in particular at least three, free isocyanate groups, or at least two, in particular at least three, free and at least one, in particular at least two, blocked isocyanate group and at least one hardening segment, preferably at least two and in particular at least three hardening segments, which increase the glass transition temperature Tg as a component of three-dimensional networks; With
• 2. at least one, in particular one, compound containing, on average, at least one, in particular one, isocyanate-reactive functional group and at least one, in particular one, reactive functional group with at least one bond which can be activated with actinic radiation in the molecule;

or it consists of these components.

Accordingly, none in this preferred embodiment Crosslinking agents (B1) and (B2) prepared and then to the Crosslinking agent component (B) combines, but it is from a mixture 1.) from polyisocyanates 1.1) and 1.2), which then with the compound 2.) implemented in a one-pot process to the crosslinking agent component (B) without isolating defined products.

The essential combination of flexibilizing and hardening According to a third preferred embodiment, segments can also be over Compounds 1.3) or 1.4) introduced into the crosslinking agent components (B) become.

The compounds 1.3) contain at least a statistical average in the molecule two, in particular two, isocyanate-reactive functional groups and at least a, especially a, hardening segment that is part of three-dimensional networks whose glass transition temperature Tg increases.

In this case, the reactants of the compounds 1.3.) Are the Polyisocyanates 1.1).

The compounds 1.4) contain at least a statistical average in the molecule two, in particular two, isocyanate-reactive functional groups and at least a, in particular a, flexible segment that is part of three-dimensional networks whose glass transition temperature Tg lowers.

In this case, the reactants of the compounds 1.4) are Polyisocyanates 1.2).

The compounds 1.3) are with the polyisocyanates 1.1) and Compounds 1.4) with the polyisocyanates 1.2) in an equivalent ratio of isocyanate-reactive functional groups converted to free isocyanate groups, that in the resulting precursors 3.) on average still in the molecule at least two, in particular at least three, free isocyanate groups or at least two, in particular at least three, free isocyanate groups and contain at least one, especially two, blocked isocyanate group (s) are.

However, precursor 3) can also be prepared by reacting the following reactants, taking into account the above conditions:
1.1) + [1.3) + 1.4)],
1.2) + [1.4) + 1.3)],
[1.1) + 1.2)] + 1.3),
[1.1) + 1.2)] + 1.4) and
[1.1) + 1.2)] + [1.3) + 1.4)].

In a further stage, the precursors 3.) with the compounds 2.) in an equivalent ratio of isocyanate-reactive functional groups to free Isocyanate groups implemented that the resulting components of the Crosslinking agent components (B) the features essential to the invention (i), (ii), (iii) and (iv). The crosslinking agent components (B) can do this Contain or consist of components.

If the coating materials according to the invention are two or Multi-component systems, contain the cross-linking agent components (B) obligatory free isocyanate groups. In addition, they can still be blocked Contain isocyanate groups.

Are the coating materials of the invention One-component systems, contain the cross-linking agent components (B) predominantly or exclusively blocked isocyanate groups.

• - Phenolen, wie Phenol, Cresol, Xylenol, Nitrophenol, Chlorophenol, Ethylphenol, tert.-Butylphenol, Hydroxybenzoesäure, Ester dieser Säure oder 2,5-di-tert.-Butyl-4-hydroxytoluol;
• - Lactamen, wie ε-Caprolactam, δ-Valerolactam, γ-Butyrolactam oder β- Propiolactam;
• - aktiven methylenischen Verbindungen, wie Diethylmalonat, Dimethylmalonat, Acetessigsäureethyl- oder -methylester oder Acetylaceton;
• - Alkoholen, wie Methanol, Ethanol, n-Propanol, Isopropanol, n-Butanol, Isobutanol, t-Butanol, n-Amylalkohol, t-Amylalkohol, Laurylalkohol, Ethylenglykolmonomethylether, Ethylenglykolmonoethylether, Ethylenglykolmonopropylether Ethylenglykolmonobutylether, Diethylenglykolmonomethylether, Diethylenglykolmonoethylether, Propylenglykolmonomethylether, Methoxymethanol, Glykolsäure, Glykolsäureester, Milchsäure, Milchsäureester, Methylolharnstoff, Methylolmelamin, Diacetonalkohol, Ethylenchlorohydrin, Ethylenbromhydrin, 1,3-Dichloro-2-propanol, 1,4-Cyclohexyldimethanol oder Acetocyanhydrin;
• - Mercaptanen, wie Butylmercaptan, Hexylmercaptan, t-Butylmercaptan, t- Dodecylmercaptan, 2-Mercaptobenzothiazol, Thiophenol, Methylthiophenol oder Ethylthiophenol;
• - Säureamiden, wie Acetoanilid, Acetoanisidinamid, Acrylamid, Methacrylamid, Essigsäureamid, Stearinsäureamid oder Benzamid;
• - Imiden, wie Succinimid, Phthalimid oder Maleimid;
• - Aminen, wie Diphenylamin, Phenylnaphthylamin, Xylidin, N-Phenylxylidin, Carbazol, Anilin, Naphthylamin, Butylamin, Dibutylamin oder Butylphenylamin;
• - Imidazolen, wie Imidazol oder 2-Ethylimidazol;
• - Harnstoffen, wie Harnstoff, Thioharnstoff, Ethylenharnstoff, Ethylenthioharnstoff oder 1,3-Diphenylharnstoff;
• - Carbamaten, wie N-Phenylcarbamidsäurephenylester oder 2-Oxazolidon;
• - Iminen, wie Ethylenimin;
• - Oximen, wie Acetonoxim, Formaldoxim, Acetaldoxim, Acetoxim, Methylethylketoxim, Diisobutylketoxim, Diacetylmonoxim, Benzophenonoxim oder Chlorohexanonoxime;
• - Salzen der schwefeligen Säure, wie Natriumbisulfit oder Kaliumbisulfit;
• - Hydroxamsäureestern, wie Benzylmethacrylohydroxamat (BMH) oder Allylmethacrylohydroxamat; oder
• - substituierte Pyrazolen, insbesondere Dimethylpyrazol, oder Triazolen; sowie
• - Gemischen dieser Blockierungsmittel,

ausgewählt. Dabei weisen die Gemische besondere Vorteile auf, weswegen sie bevorzugt verwendet werden. Besonders bevorzugt sind die Gemische aus Malonestern und Acetessigsäureestern sowie Dimethylpyrazolen und Succinimiden. Afs blocking agents for the isocyanate groups are all customary and known blocking agents. The blocking agents are preferably selected from the group consisting of

• - Phenols, such as phenol, cresol, xylenol, nitrophenol, chlorophenol, ethylphenol, tert-butylphenol, hydroxybenzoic acid, esters of this acid or 2,5-di-tert-butyl-4-hydroxytoluene;
• Lactams, such as ε-caprolactam, δ-valerolactam, γ-butyrolactam or β-propiolactam;
• - Active methylenic compounds, such as diethyl malonate, dimethyl malonate, ethyl or methyl acetoacetate or acetylacetone;
• - Alcohols, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, n-amyl alcohol, t-amyl alcohol, lauryl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, methylene glycol ether, methylene glycol ether , Glycolic acid ester, lactic acid, lactic acid ester, methylolurea, methylolmelamine, diacetone alcohol, ethylene chlorohydrin, ethylene bromohydrin, 1,3-dichloro-2-propanol, 1,4-cyclohexyldimethanol or acetocyanhydrin;
• Mercaptans, such as butyl mercaptan, hexyl mercaptan, t-butyl mercaptan, t-dodecyl mercaptan, 2-mercaptobenzothiazole, thiophenol, methylthiophenol or ethylthiophenol;
• - Acid amides, such as acetoanilide, acetoanisidinamide, acrylamide, methacrylamide, acetic acid amide, stearic acid amide or benzamide;
• Imides such as succinimide, phthalimide or maleimide;
• Amines such as diphenylamine, phenylnaphthylamine, xylidine, N-phenylxylidine, carbazole, aniline, naphthylamine, butylamine, dibutylamine or butylphenylamine;
• Imidazoles, such as imidazole or 2-ethylimidazole;
• Ureas, such as urea, thiourea, ethylene urea, ethylene thiourea or 1,3-diphenylurea;
• Carbamates, such as phenyl N-phenylcarbamate or 2-oxazolidone;
• - Imines, such as ethyleneimine;
• Oximes, such as acetone oxime, formal doxime, acetaldoxime, acetoxime, methyl ethyl ketoxime, diisobutyl ketoxime, diacetyl monoxime, benzophenone oxime or chlorohexanone oxime;
• - Sulfuric acid salts such as sodium bisulfite or potassium bisulfite;
• Hydroxamic acid esters, such as benzyl methacrylohydroxamate (BMH) or allyl methacrylohydroxamate; or
• - substituted pyrazoles, especially dimethylpyrazole, or triazoles; such as
• Mixtures of these blocking agents,

selected. The mixtures have particular advantages, which is why they are preferably used. The mixtures of malonic esters and acetoacetic acid esters as well as dimethylpyrazoles and succinimides are particularly preferred.

The crosslinking agent components (B) contain reactive functional groups with at least one bond that can be activated with actinic radiation.

Examples of suitable bonds which can be activated with actinic radiation are Carbon-hydrogen single bonds or carbon-carbon, Carbon-oxygen, carbon-nitrogen, carbon-phosphorus or Carbon-silicon single bonds or double bonds. Of these will be the double bonds, especially the carbon-carbon double bonds (hereinafter referred to as "double bonds", preferably used.

Suitable double bonds are, for example, in (meth) acrylate, Ethacrylate, crotonate, cinnamate, vinyl ether, vinyl ester, ethenylarylene, Dicyclopentadienyl, norbornenyl, isoprenyl, isoprenyl, isopropenyl, allyl or butenyl; Ethenylarylene, dicyclopentadienyl, norbornenyl, isoprenyl, Isopropenyl, allyl or butenyl ether groups or ethenylarylene, Dicyclopentadienyl, norbornenyl, isoprenyl, isopropenyl, allyl or Butenyl ester groups. Of these, (meth) are acrylate groups, in particular Acrylate groups, of particular advantage and are therefore according to the invention used very particularly preferably.

• - Allylalkohol oder 4-Butylvinylether;
• - Hydroxyalkylester und Hydroxycycloalkylester der Acrylsäure oder der Methacrylsäure, insbesondere der Acrylsäure, die durch Veresterung aliphatischer Diole, beispielsweise der vorstehend beschriebenen niedermolekularen Diole B), mit Acrylsäure oder Methacrylsäure oder durch Umsetzung von Acrylsäure oder Methacrylsäure mit einem Alkylenoxid erhältlich sind, insbesondere Hydroxyalkylester der Acrylsäure oder Methacrylsäure, in denen die Hydroxyalkylgruppe bis zu 20 Kohlenstoffatome enthält, wie 2-Hydroxyethyl-, 2-Hydroxypropyl-, 3- Hydroxypropyl-, 3-Hydroxybutyl-, 4-Hydroxybutyl-, Bis(hydroxymethyl)cyclohexanacrylat oder -methacrylat; von diesen sind 2- Hydroxyethylacrylat und 4-Hydroxybutylacrylat besonders vorteilhaft und werden deshalb erfindungsgemäß besonders bevorzugt verwendet; oder
• - Umsetzungsprodukte aus cyclischen Estern, wie z. B. epsilon-Caprolacton, und diesen Hydroxyalkyl- oder -cycloalkylestern.

Suitable compounds 2.) by means of which the reactive functional groups described above with at least one bond which can be activated with actinic radiation can be introduced into the crosslinking agent components (B) contain at least one, in particular one, isocyanate-reactive functional group and at least one, in particular one, with Binding per molecule that can be activated by actinic radiation. Examples of suitable compounds of this type are

• - Allyl alcohol or 4-butyl vinyl ether;
• - Hydroxyalkyl esters and hydroxycycloalkyl esters of acrylic acid or methacrylic acid, in particular acrylic acid, which can be obtained by esterifying aliphatic diols, for example the low-molecular diols B) described above, with acrylic acid or methacrylic acid or by reacting acrylic acid or methacrylic acid with an alkylene oxide, in particular hydroxyalkyl esters of acrylic acid or methacrylic acid in which the hydroxyalkyl group contains up to 20 carbon atoms, such as 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 3-hydroxybutyl, 4-hydroxybutyl, bis (hydroxymethyl) cyclohexane acrylate or methacrylate; Of these, 2-hydroxyethyl acrylate and 4-hydroxybutyl acrylate are particularly advantageous and are therefore used with particular preference in accordance with the invention; or
• - Reaction products from cyclic esters, such as. B. epsilon-caprolactone, and these hydroxyalkyl or cycloalkyl esters.

The crosslinking agent component (B) or the one described above Base products contain the flexibilizing segments that are part of it three-dimensional networks lower their glass transition temperature Tg.

The flexibilizing segments are preferably double-bonded organic residues. The flexibilizing segments from the group consisting of are preferred double-bonded aliphatic hydrocarbon residues and double-bonded Aliphatic hydrocarbon radicals containing heteroatoms.

Examples of suitable flexibilizing, double-bonded organic residues of this type are substituted or unsubstituted, preferably unsubstituted, linear or branched, preferably linear, alkanediyl radicals with 4 to 30, preferably 5 to 20 and especially 6 carbon atoms within the carbon chain as well may contain cyclic groups, provided that the carbon chains between the Isocyanate groups and the cyclic groups each more than two Contain carbon atoms.

Examples of suitable linear alkanediyl radicals are tetramethylene, Pentamethylene, hexamethylene, heptamethylene, octamethylene, nonane-1,9-diyl, Decane-1,10-diyl, undecane-1,11-diyl dodecane-1,12-diyl, tridecane-1,13-diyl, Tetradecane-1,14-diyl, pentadecane-1,15-diyl, hexadecane-1,16-diyl, heptadecane 1,17-diyl, octadecane-1,18-diyl, nonadecane-1,19-diyl or eicosan-1,20-diyl, preferably tetramethylene, pentamethylene, hexamethylene, heptamethylene, Octamethylene, nonane-1,9-diyl, decane-1,10-diyl, especially hexamethylene.

Examples of well-suited alkanediyl residues in the carbon chain too contain cyclic groups are 2-heptyl-1-pentyl-cyclohexane-3,4-bis (non-9-yl), Cyclohexan-1,2-, 1,4- or -1,3-bis (eth-2-yl), cyclohexan-1,3-bis (prop-3-yl) or Cyclohexan-1,2-, 1,4- or 1,3-bis (but-4-yl).

Further examples of suitable divalent organic radicals which contain heteroatoms are divalent polyester radicals with recurring polyester fractions of the formula - (- CO- (CHR ⁵ ) _m -CH ₂ -O -) - from. The index m is preferably 4 to 6 and the substituent R ⁵ = hydrogen, an alkyl, cycloalkyl or alkoxy radical. No substituent contains more than 12 carbon atoms.

Further examples of suitable divalent organic radicals which contain heteroatoms are divalent linear polyether radicals, preferably with a number average molecular weight of 400 to 5,000, in particular of 400 tris 3,000. Highly suitable polyether radicals have the general formula - (- O- (CHR ⁶ ) _o -) _p O-, where the substituent R ⁶ = hydrogen or a lower, optionally substituted alkyl radical, the index o = 2 to 6, preferably 3 to 4, and the index p = 2 to 100, preferably 5 to 50. Linear or branched polyether radicals derived from poly (oxyethylene) glycols, poly (oxypropylene) glycols and poly (oxybutylene) glycols are mentioned as particularly suitable examples.

There are also linear double-bonded siloxane residues such as these for example in silicone rubbers, hydrogenated polybutadiene or Polyisoprene residues, statistical or alternating butadiene-isoprene Copolymer residues or butadiene-isoprene graft copolymer residues that still Polymerized styrene can contain, as well as ethylene propylene diene residues in Consideration.

All organic functional groups come into consideration as substitutes, which are essentially inert, i.e. that is, they have no reactions with the Components of the coating materials according to the invention.

Examples of suitable inert organic radicals are alkyl groups, in particular Methyl groups, halogen atoms, nitro groups, nitrile groups or alkoxy groups. Of the divalent organic radicals described above, the Alkanediyl residues that have no substituents and no cyclic groups in the Contain carbon chain, advantageous and are therefore preferably used.

Crosslinking agent (B 1) or part of the crosslinking agent components (B) are expediently prepared from polyisocyanates 1.1). these can contain the same or different flexibilizing segments. Preferably they contain flexibilizing segments of the same kind.

The polyisocyanates 1.1) preferably have an isocyanate functionality> 2, preferably> 2.5, particularly preferably> 2.7 and in particular> 2.9. The upper The limit of the isocyanate functionality is preferably 10, preferably 8, very particularly preferably at 6 and in particular at 5.

Examples of suitable polyisocyanates 1.1) are the oligomers of diisocyanates, such as trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, Hexamethylene diisocyanate, heptamethylene diisocyanate, ethylethylene diisocyanate, Trimethylhexane diisocyanate or acyclic aliphatic diisocyanates, the one contain cyclic groups in their carbon chain, such as diisocyanates of dimer fatty acids, such as those sold under the trade name DDI 1410 by Henkel sold and in the patents WO 97/49745 and WO 97/49747 can be described, in particular 2-heptyl-3,4-bis (9-isocyanatononyl) - 1-pentyl-cyclohexane, or 1,2-, 1,4- or 1,3-bis (2-isocyanatoeth-1-yl) cyclohexane, 1,3-bis (3-isocyanatoprop-1-yl) cyclohexane or 1,2-, 1,4- or 1,3-bis (4- isocyanatobut-1-yl) cyclohexane. The latter are within the scope of the present Invention because of their two bound exclusively to alkyl groups Isocyanate groups despite their cyclic groups to the acyclic aliphatic Counting diisocyanates. Of these diisocyanates Hexamethylene diisocyanate is particularly preferably used.

Oligomers 1.1) are preferably used, the isocyanurate, urea, Urethane, biuret, uretdione, iminooxadiazinedione, carbodiimide and / or Allophanate groups included. Examples of suitable manufacturing processes are from the patents CA 2,163,591 A, US 4,419,513 A, US 4,454,317 A, EP 0 646 608 A, US 4,801,675 A, EP 0 183 976 A1, DE 40 15 155 A1, EP 0 303 150 A1, EP 0 496 208 A1, EP 0 524 500 A1, EP 0 566 037 A1, US 5,258,482 A1, US 5,290,902 A1, EP 0 649 806 A1, DE 42 29 183 A1 or EP 0 531 820 A1 known or they are in the unpublished German Patent application DE 10 00 5228.2 described.

In addition, nonyl triisocyanate (NTI) is also suitable as polyisocyanate 1.1).

The crosslinking agent components (B) or the crosslinking agent (B 2) contain the hardening segments as part of three-dimensional Networks whose glass transition temperature Tg increase.

The hardening segments are bi- or multi-bonded organic residues. Divalent organic radicals are preferably used. Next to it in minor quantities multi-binding, especially triple-binding, organic Residues are used by which the crosslink density is influenced can.

• - zweibindige aromatische, cycloaliphatische und aromatischcycloaliphatische Reste, bei denen innerhalb der Vernetzungsmittel (B 2) und in den Polyisocyanaten 1.2) mindestens eine verknüpfende Bindung direkt zur cycloaliphatischen und/oder aromatischen Struktureinheit führt,
• - sowie zweibindige alphatische Reste, bei denen innerhalb der Vernetzungsmittel (B 2) und in den Polyisocyanaten 1.2) die beiden verknüpfenden Bindungen zu Methylengruppen führen, die mit einer aromatischen oder cycloaliphatischen, insbesondere cycloaliphatischen, Struktureinheit verbunden sind.

Examples of well suited hardening segments are

• divalent aromatic, cycloaliphatic and aromaticcycloaliphatic radicals in which at least one linking bond leads directly to the cycloaliphatic and / or aromatic structural unit within the crosslinking agent (B 2) and in the polyisocyanates 1.2),
• - As well as double-bonded alphatic radicals in which within the crosslinking agent (B 2) and in the polyisocyanates 1.2) the two linking bonds lead to methylene groups which are linked to an aromatic or cycloaliphatic, in particular cycloaliphatic, structural unit.

The double-bonded cycloaliphatic, aromatic and aliphatic, in particular the cycloaliphatic radicals are advantageous and are preferred used.

Examples of suitable divalent aromatic radicals are substituted, in particular methyl-substituted or unsubstituted aromatic radicals with 6 to 30 carbon atoms in the molecule, such as phen-1,4-, 1,3-or -1,2-ylene, naphth-1,4-, -1,3-, -1,2-, -1,5- or -2,5-ylene, propan-2,2-di (phen-4'-yl), methane-di (phen-4'- yl) Diphenyl-4,4'-diyl or 2,4- or 2,6-tolylene.

Examples of suitable divalent cycloaliphatic radicals are substituted or unsubstituted, preferably unsubstituted, cycloalkanediyl radicals with 4 to 20 Carbon atoms, such as cyclobutane-1,3-diyl, cyclopentane-1,3-diyl, cyclohexane 1,3- or -1,4-diyl, cycloheptane-1,4-diyl, norbornane-1,4-diyl, adamantane-1,5-diyl, Decalin-diyl, 3,3,5-trimethyl-cyclohexane-1,5-diyl, 1-methylcyclohexane-2,6-diyli, Dicyclohexylmethane-4,4'-diyl, 1,1'-dicyclohexane-4,4'-diyl or 1,4- Dicyclohexylhexane-4,4 "-diyl, in particular 3,3,5-trimethyl-cyclohexane-1,5-diyl or dicyclohexylmethane-4,4'-diyl. In addition, in minor quantities the corresponding triyl radicals are used.

Examples of suitable aliphatic radicals are cyclohexane-1,2-, -1,4- or -1,3- bis (methyl).

Examples of suitable substituents are those described above.

Crosslinking agent (B 2) or part of the crosslinking agent components (B) are expediently prepared from polyisocyanates 1.2). these can contain the same or different hardening segments. Preferably they contain hardening segments of the same type.

The polyisocyanates 1.2) preferably have an isocyanate functionality> 2, preferably> 2.5, particularly preferably> 2.7 and in particular> 2.9. The upper The limit of the isocyanate functionality is preferably 10, preferably 8, very particularly preferably at 6 and in particular at 5.

Examples of suitable polyisocyanates 1.2) are the oligomers of diisocyanates, like isophorone diisocyanate (= 5-isocyanato-1-isocyanatomethyl-1,3,3-trimethyl- cyclohexane), 5-isocyanato-1- (2-isocyanatoeth-1-yi) -1,3,3-trimethyl-cyclohexane, 5- Isocyanato-1- (3-isocyanatoprop-1-yl) -1,3,3-trimethyl-cyclohexane, 5-isocyanato- (4- isocyanatobut-1-yl) -1,3,3-trimethyl-cyclohexane, 1-isocyanato-2- (3-isocyanatoprop- 1-yl) -cyclohexane, 1-isocyanato-2- (3-isocyanatoeth-1-yl) cyclohexane, 1-isocyanato- 2- (4-isocyanatobut-1-yl) cyclohexane, 1,2-diisocyanatocyclobutane, 1,3- Diisocyanatocyclobutane, 1,2-diisocyanatocyclopentane, 1,3- Diisocyanatocyclopentane, 1,2-diisocyanatocyclohexane, 1,3- Diisocyanatocyclohexane, 1,4-diisocyanatocyclohexane, 1,2-, 1,4- or 1,3- Bis (isocyanatomethyl) cyclohexane, dicyclohexylmethane-2,4'-diisocyanate or Dicyclohexylmethane-4,4'-diisocyanate, especially isophorone diisocyanate.

Oligomers 1.2) are preferably used, the isocyanurate, urea, Urethane, biuret, uretdione, iminooxadiazinedione, carbodiimide and / or Allophanate groups included. Examples of suitable manufacturing processes are from the patents CA 2,163,591 A, US 4,419,513 A, US 4,454,317 A, EP 0 646 608 A, US 4,801,675 A, EP 0 183 976 A1, DE 40 15 155 A1, EP 0 303 150 A1, EP 0 496 208 A1, EP 0 524 500 A1, EP 0 566 037 A1, US 5,258,482 A1, US 5,290,902 A1, EP 0 649 806 A1, DE 42 29 183 A1 or EP 0 531 820 A1 known or they are in the unpublished German Patent application DE 10 00 5228.2 described.

The crosslinking agents (B1) are known compounds and are for example in European patent application EP 0 928 800 A1, in particular page 4, lines 41 to 54. They are also from sold by Bayer AG under the Roskydal® UA VPLS 2337 brand.

The crosslinking agents (B2) are also known compounds and are, for example, according to European patent application EP 0 928 800 A1, especially page 4, lines 41 to 54, only that instead of there used oligomers 1.1) of hexamethylene diisocyanate an oligomer 1.2) of Isophorone diisocyanate is used.

In the crosslinking agent components (B) to be used according to the invention the weight ratio of crosslinking agent (B1) to crosslinking agent (B2) vary widely. The weight ratio (B1): (B2) mainly depends according to which property profile the three-dimensional built from it Network of coatings. So affect the flexibilizing Segments of crosslinking agents (B1) especially the scratch resistance of the Coatings, whereas the hardening segments of the crosslinking agents (B2) mainly affect the hardness of the coatings. Surprisingly can also have a high weight ratio (B1): (B2) Scratch resistance and a high etch resistance can be set.

The weight ratio (B1): (B2) is preferably from 10: 1 to 1: 5, preferably 9: 1 to 1: 3, particularly preferably 8: 1 to 1: 2, very particularly preferably 6: 1 to 1: 1 and in particular 5: 1 to 1: 1.

Are the crosslinking agent components (B) by implementing one of the Mixtures 1.) prepared above, the ratio of Polyisocyanates 1.1) and 1.2) are preferably adjusted so that they can be calculated likewise result in the weight ratios described above.

Suitable compounds 1.3), through the hardening segments in the Crosslinking agent components (B) according to the third preferred Embodiment are introduced from the group consisting of Polyols, especially diols, polyamines, especially diamines, and Amino alcohols selected. From this point the diamines and the diols special advantages and are therefore preferred.

Preferred diols and diamines are selected from the group consisting of Cyclobutane-1,3-diol, cyclopentane-1,3-diol, cyclohexane-1,3- or -1,4-diol, Cycloheptane-1,4-diol, norbornane-1,4-diol, adamantane-1,5-diol, decalin diol, 3,3,5- Trimethyl-cyclohexane-1,5-diol, 1-methylcyclohexane-2,6-diol, dicyclohexylmethane 4,4'-diol, 1,1'-dicyclohexane-4,4'-diol or 1,4-dicyclohexylhexane-4,4 "diol, in particular 3,3,5-trimethyl-cyclohexane-1,5-diol or dicyclohexylmethane-4,4'- diol and the corresponding diamines.

Suitable compounds 1.4), through the flexibilizing segments in the Crosslinking agent components (B) according to the third preferred Embodiment are also introduced from the group consisting from polyols, in particular diols, polyamines, in particular diamines, and Amino alcohols selected. From this point the diamines and the diols special advantages and are therefore preferred.

• - Butan-1,4-, Pentan-1,5-, Hexan-1,6-, Heptan-1,7-, Octan-1,8-, Nonan-1,9-, Decan-1,10-, Undecan-1,11-, Dodecan-1,12-, Tridecan-1,13-, Tetradecan- 1,14-, Pentadecan-1,15-, Hexadecan-1,16-, Heptadecan-1,17-, Octadecan- 1,18-, Nonadecan-1,19- oder Eicosan-1,20-diol, sowie den entsprechenden Diaminen;
• - 2-Heptyl-1-pentyl-cyclohexan-3,4-bis(nonyl-9-ol), Cyclohexan-1,2-, -1,4- oder -1,3-bis(methylol), Cyclohexan-1,2-, 1,4- oder -1,3-bis(ethyl-2-ol), Cyclohexan-1,3-bis(propyl-3-ol) oder Cyclohexan-1,2-, 1,4- oder 1,3- bis(butyi-4-ol), sowie den entsprechenden Diaminen;
• - Diolen und Diaminen auf der Basis zweiwertiger Polyesterreste mit wiederkehrenden Polyesteranteilen der Formel -(-CO-(CHR⁵)_m-CH₂O-)- aus; hierbei ist der Index m bevorzugt 4 bis 6 und der Substitutent R⁵ = Wasserstoff, ein Alkyl-, Cycloalkyl- oder Alkoxy-Rest. Kein Substituent enthält mehr als 12 Kohlenstoffatome, sowie
• - Diolen und Diaminen auf der Basis zweiwertiger linearer Polyetherreste, vorzugsweise mit einem zahlenmittleren Molekulargewicht von 400 bis 5.000, insbesondere von 400 bis 3.000; insbesondere Polyetherreste der allgemeine Formel -(-O-(CHR⁶)_o-)_pO-, wobei der Substituent R⁵ = Wasserstoff oder ein niedriger, gegebenenfalls substituierter Alkylrest ist, der Index o = 2 bis 6, bevorzugt 3 bis 4, und der Index p = 2 bis 100, bevorzugt 5 bis 50, ist; speziell Polyetherreste, die sich von Poly(oxyethylen)glykolen, Poly(oxypropylen)glykolen und Poly(oxybutylen)glykolen ableiten;

ausgewählt. Preferred diols and diamines are selected from the group consisting of

• - 1,4-butane, 1,5-pentane, 1,6-hexane, 1,7-heptane, 1,8-octane, 1,9-nonane, 1,10-decane, Undecane-1.11-, Dodecane-1.12-, Tridecane-1.13-, Tetradecane-1.14-, Pentadecane-1.15-, Hexadecane-1.16-, Heptadecane-1.17-, Octadecane - 1,18-, nonadecane-1,19- or eicosane-1,20-diol, as well as the corresponding diamines;
• - 2-heptyl-1-pentyl-cyclohexane-3,4-bis (nonyl-9-ol), cyclohexane-1,2-, -1,4- or -1,3-bis (methylol), cyclohexane-1 , 2-, 1,4- or -1,3-bis (ethyl-2-ol), cyclohexane-1,3-bis (propyl-3-ol) or cyclohexane-1,2-, 1,4- or 1,3- bis (butyi-4-ol) and the corresponding diamines;
• - Diols and diamines based on divalent polyester residues with recurring polyester components of the formula - (- CO- (CHR ⁵ ) _m -CH ₂ O -) - from; the index m is preferably 4 to 6 and the substituent R ⁵ = hydrogen, an alkyl, cycloalkyl or alkoxy radical. No substituent contains more than 12 carbon atoms, as well
• - Diols and diamines based on divalent linear polyether residues, preferably with a number average molecular weight from 400 to 5,000, in particular from 400 to 3,000; in particular polyether radicals of the general formula - (- O- (CHR ⁶ ) _o -) _p O-, where the substituent R ⁵ = hydrogen or a lower, optionally substituted alkyl radical, the index o = 2 to 6, preferably 3 to 4, and the index p = 2 to 100, preferably 5 to 50; especially polyether residues derived from poly (oxyethylene) glycols, poly (oxypropylene) glycols and poly (oxybutylene) glycols;

selected.

For use in aqueous coating materials according to the invention the crosslinking agent components (B) described above in can be modified hydrophilically in the usual and known manner, for example by ionic groups such as carboxylate groups or quaternary ammonium groups in the molecules are incorporated.

The proportion of the crosslinking agent components (B) in the inventive Coating materials can vary very widely and depend primarily on the Number of isocyanate-reactive functional groups in the binders (A) on the one hand and the number of free and / or unblocked isocyanate groups in the crosslinking agent components (B) on the other hand. Preferably the Proportion of (B) chosen so that there is an equivalent ratio of isocyanate-reactive functional groups to free and / or blocked isocyanate groups of 2: 1 to 1: 2, preferably 1.8: 1 to 1: 1.8, particularly preferably 1.6: 1 to 1: 1.6, entirely particularly preferably 1.4: 1 to 1: 1.4 and in particular 1.2: 1 to 1: 1.2 established. In general, the content of the invention is then Coating materials on the crosslinking agent components (B) preferably at 10 to 80, preferably 15 to 75, particularly preferably 20 to 70, very particularly preferably 25 to 65 and in particular 30 to 60% by weight, in each case based on the Solids of the coating material of the invention.

In addition to the essential components (A) and (B) described above the coating materials of the invention can also have at least one actinic radiation activatable component (C) by the above described crosslinker component (B) is different. The Component (C) can also be at least one isocyanate-reactive functional Group, in particular contain at least one hydroxyl group.

Examples of suitable components (C) which can be activated with actinic radiation are low molecular weight reactive thinners and oligomeric or polymeric acrylate-functional (meth) acrylic copolymers, polyether acrylates, polyester acrylates, polyesters, Epoxy acrylates, urethane acrylates, amino acrylates, melamine acrylates, silicone acrylates and phosphazene acrylates and the corresponding methacrylates as they for example from German patent applications DE 197 09 467 A1, or DE 198 18 735 A1 or in the German patent DE 197 09 467 C 2 known are. Urethane (meth) acrylates, such as those made of, for example, are particularly preferred are known from European patent application EP 0 204161 A1, Reactive thinner with at least four acrylate groups, such as those made of German patent application DE 198 18 735 A1, column 7, lines 1 to 25, are known, or dipentaerythritol pentaacrylate.

If they are used, they can be activated with actinic radiation Components (C) in the coating materials of the invention in one Amount of 1 to 50, preferably 2 to 45, preferably 3 to 40 and in particular 4 to 35 wt .-%, each based on the solid of the invention Coating material included.

In addition to the ingredients described above, the coating materials according to the invention also at least one pigment (D) contain.

In the case of two- and multi-component systems, the pigments (D) via the binder component (A) and / or the crosslinking agent component (B) can be mixed in. Preferably they are about Binder component (A) mixed.

The pigments (D) from the group consisting of color and / or effect, fluorescent, electrically conductive and magnetic shielding pigments, metal powders, organic and inorganic, transparent and opaque fillers and nanoparticles (in summary "Pigments" selected) selected.

Examples of suitable effect pigments (D) are metal plate pigments such as commercially available aluminum bronzes, chromated according to DE 36 36 183 A1 Aluminum bronze, and commercially available stainless steel bronze and non-metallic Effect pigments, such as pearlescent or interference pigments, platelet-like effect pigments based on iron oxide, which has a hue from pink to brownish red or liquid crystalline effect pigments. additional is applied to Römpp Lexicon Lacke und Druckfarben, Georg Thieme Verlag, 1998, Pages 176, "Effect Pigments" and Pages 380 and 381 "Metal Oxide Mica Pigments "to" Metal Pigments ", and the patent applications and patents DE 36 36 156 A1, DE 37 18 446 A1, DE 37 19 804 A1, DE 39 30 601 A1, EP 0 068 311 A1, EP 0 264 843 A1, EP 0 265 820 A1, EP 0 283 852 A1, EP 0 293 746 A1, EP 0 417 567 A1, US 4,828,826 A or US 5,244,649 A.

Examples of suitable inorganic coloring pigments (D) are White pigments such as titanium dioxide, zinc white, zinc sulfide or lithopone; Black pigments such as carbon black, iron-manganese black or spinel black;

Colored pigments such as chromium oxide, chromium oxide hydrate green, cobalt green or Ultramarine green, cobalt blue, ultramarine blue or manganese blue, ultramarine violet or cobalt and manganese violet, iron oxide red, cadmium sulfoselenide, molybdate red or ultramarine red; Iron oxide brown, mixed brown, spinel and corundum phases or Chrome orange; or iron oxide yellow, nickel titanium yellow, chrome titanium yellow, Cadmium sulfide, cadmium zinc sulfide, chrome yellow or bismuth vanadate.

Examples of suitable organic coloring pigments (D) are Monoazo pigments, bisazo pigments, anthraquinone pigments, Benzimidazole pigments, quinacridone pigments, quinophthalone pigments, Diketopyrrolopyrrole pigments, dioxazine pigments, indanthrone pigments, Isoindoline pigments, isoindolinone pigments, azomethine pigments, Thioindigo pigments, metal complex pigments, perinone pigments, perylene pigments, Phthalocyanine pigments or aniline black.

In addition, varnish and printing inks are used on Römpp Lexikon, Georg Thieme Verlag, 1998, pages 180 and 181, "Eisenblau-Pigments" to "Eisenoxidschwarz", pages 451 to 453 "Pigments" to "Pigment Volume Concentration", page 563 "Thioindigo Pigments", page 567 "Titanium dioxide pigments", pages 400 and 467, "Naturally occurring Pigments ", page 459" Polycyclic Pigments ", page 52," Azomethine Pigments "," Azo Pigments ", and page 379," Metal Complex Pigments ", directed.

Examples of fluorescent pigments (D) (daylight pigments) are Bis (azomethine) pigments.

Examples of suitable electrically conductive pigments (D) are Titanium dioxide / tin oxide pigments.

Examples of magnetically shielding pigments (D) are pigments based on them of iron oxides or chromium dioxide.

Examples of suitable metal powders (D) are powders of metals and Metal alloys aluminum, zinc, copper, bronze or brass.

Examples of suitable organic and inorganic fillers (D) are chalk, Calcium sulfate, barium sulfate, silicates such as talc, mica or kaolin, Silicas, oxides such as aluminum hydroxide or magnesium hydroxide or organic fillers such as plastic powder, in particular made of polyamide or Polyacrylonitrile. In addition, varnish and printing inks, Georg, are added to Römpp Lexikon Thieme Verlag, 1998, pages 250 ff., "Fillers".

It is also advantageous to use mixtures (D) of platelet-shaped inorganic Fillers such as talc or mica and non-platelet-shaped inorganic To use fillers such as chalk, dolomite, calcium sulfate or barium sulfate, because it sets the viscosity and flow behavior very well can.

Examples of suitable transparent fillers (D) are those based on Silicon dioxide, aluminum oxide or zirconium oxide.

Suitable nanoparticles (D) are selected from the group consisting of hydrophilic and hydrophobic, especially hydrophilic, nanoparticles on the Base of silicon dioxide, aluminum oxide, zinc oxide, zirconium oxide and the Polyacids and heteropolyacids of transition metals, preferably of Molybdenum and tungsten, with a primary article size <50 nm, preferably 5 to 50 nm, in particular 10 to 30 nm. The hydrophilic ones are preferred Nanoparticles no matting effect. Nanoparticles are particularly preferred used on the basis of silicon dioxide.

Hydrophilic fumed silicas are very particularly preferred used, whose agglomerates and aggregates have a chain-like structure and that through the flame hydrolysis of silicon tetrachloride in one Oxyhydrogen flame can be produced. These are used, for example, by the company Degussa sold under the brand Aerosil®. Be particularly preferred also precipitated water glasses, such as nano-hectorite, for example from the company Südchemie under the Optigel® brand or from Laporte under the brand Laponite® are used.

The pigment content of the coating materials according to the invention (D) can vary widely. The content is preferably adjusted so that a Pigment-binder ratio (D): (A) from 1:10 to 5: 1, preferably 1: 8 to 4.5: 1, particularly preferably 1: 6 to 4: 1, very particularly preferably 1: 4 to 3.5: 1 and in particular 1: 2 to 3: 1 results.

Instead of or in addition to the pigments described above (D) the coating materials of the invention can also have at least one Contain additive (E). In the case of two or more component systems the additives (E) via the binder component (A) and / or Crosslinking agent component (B) are mixed. Preferably they will mixed in via the binder component (A).

Examples of suitable additives (E) are physically curable binders which are different from the binders (A) described above; of the Various crosslinking agent components (B) described above Crosslinking agent; molecularly dispersible dyes; Sunscreen such as UV absorber and reversible radical scavenger (HALS); antioxidants; low and high-boiling ("long") organic solvents; Venting means; Wetting agents; emulsifiers; slip additives; polymerization inhibitors; Catalysts for the thermal crosslinking; thermolabile radical initiators; Photoinitiators and photocoinitiators; thermally curable reactive thinners; Adhesion promoters; Leveling agents; film-forming aids; Rheology aids (thickener and pseudoplastic sag control agents, SCA); Flame retardants; Corrosion inhibitors; anti-caking agents; waxes; driers; Biocides and / or matting agents; such as in the textbook "Lackadditive" by Johan Bieleman, Wiley-VCH, Weinheim, New York, 1998, in German patent application DE 199 14 896 A1, column 14, Page 26, until column 15, line 46, are described in detail. Complementary still refer to DE 199 04 317 A1 and DE 198 55 125 A1.

Methodically, the production of the coating materials according to the invention no special features, but is done by mixing and Homogenize the components described above using conventional and known mixing processes and devices such as stirred kettles, agitator mills, Extruders, kneaders, Ultraturrax, in-line dissolvers, static mixers, Sprocket dispersers, pressure relief nozzles and / or microfluidizers preferably with the exclusion of actinic radiation.

The resulting coating materials of the invention are conventional coating materials containing organic solvents, aqueous Coating materials, essentially or completely free of solvents and water liquid coating materials (100% systems), essentially or completely Solvent- and water-free solid coating materials (powder coatings) or in essential or completely solvent-free powder coating suspensions (powder slurries).

They are excellent for producing single and multi-layer clear coats, as well as single and multi-layer, color and / or effect, electrical conductive, magnetically shielding and / or fluorescent coatings particularly suitable according to the wet-on-wet method in which a basecoat, in particular a waterborne basecoat, applied to the surface of a substrate after which the resulting basecoat film is cured without curing dries and covered with a clear coat. Then the both layers hardened together.

Surprisingly, the coating materials of the invention are also as Suitable adhesives and sealants.

Methodically, the application of the coating materials of the invention Adhesives and sealants have no special features, but can pass through all usual application methods, such as B. spraying, knife coating, brushing, pouring, Dip, trickle or roll. Preferably, the Coating materials according to the invention spray application methods applied, unless it is powder coatings, for example with With the help of fluidized bed processes typical of powder coating. As a general rule it is advisable to work in the absence of actinic radiation in order to premature crosslinking of the coating materials and adhesives according to the invention and sealants to avoid.

Suitable substrates are all those whose surface is due to the application of heat and actinic radiation during the curing of those on it Layers is not damaged. The substrates preferably consist of Metals, plastics, wood, ceramics, stone, textiles, fiber composites, leather, glass, Glass fibers, glass and rock wool, mineral and resin-bound building materials, such as Gypsum and cement boards or roof tiles, as well as composites of these materials.

Accordingly, the coating materials, adhesives and Sealants excellent for coating, gluing and that Sealing of motor vehicle bodies parts of motor vehicle bodies, Motor vehicles indoors and outdoors, buildings indoors and Exterior, doors, windows and furniture as well as for painting, gluing and sealing in the context of industrial painting, for example Small parts, such as nuts, screws, figs or hubcaps, from coils, Containers, packaging, electrotechnical components, such as motor windings or Transformer windings, and of white goods, such as household appliances, boilers and radiators.

In the case of electrically conductive substrates, primers can be used which are produced in a customary and known manner from electrocoat materials. Both anodic and cathodic electrodeposition coatings are used for this, but especially cathodic electrocoat materials. In case of Non-functionalized and / or non-polar plastic surfaces can do this the coating in a known manner a pretreatment, such as with a plasma or with flame, subjected to or provided with a hydro primer become.

The curing of the applied dual-cure mixtures according to the invention also shows no methodological particularities, but takes place according to the usual and known thermal methods, such as heating in a forced air oven or Irradiate with IR lamps. Come for curing with actinic radiation Radiation sources such as high or low pressure mercury vapor lamps, which are optionally doped with lead to close a radiation window up to 405 nm open, or consider electron beam sources. More examples more suitable Methods and devices for curing with actinic radiation are in the German patent application DE 198 18 735 A1, column 10, lines 31 to 61, described.

The resulting coatings of the invention, especially the single-layer or multi-layer color and / or effect according to the invention Coatings and clearcoats are easy to produce and display excellent optical properties and a very high light, chemical, Water, condensation, weather and etch resistance. In particular, they are free from cloudiness and inhomogeneities. You assign one very good reflow behavior and excellent scratch resistance.

The adhesive layers according to the invention combine the most diverse Substrates adhere to each other permanently and have a high chemical and mechanical stability even at extreme temperatures and / or Temperatures fluctuations.

Likewise, the seals according to the invention permanently seal the substrates from, they have a high chemical and mechanical stability even at extreme Temperatures and / or temperature fluctuations also i. V. m. the impact aggressive chemicals.

Above all, the coatings according to the invention have a high hardness, Etch resistance and scratch resistance, which is why they are particularly advantageous can be used in the field of automotive painting.

Another advantage of the coating materials, adhesives and - Sealants is that they are more complex shaped even in the shadow areas three-dimensional substrates such as bodies, radiators or electrical Winding goods, even without optimal, in particular complete, illumination of the Shadow zones with actinic radiation coatings, adhesive layers and Deliver seals whose application-related property profile matches that of Coatings, adhesive layers and seals outside the shadow zones at least approached. This will make those in the shadow zones Coatings, adhesive layers and seals are also no longer easy to get through mechanical and / or chemical impact damaged, for example when installing further components of motor vehicles in the coated Bodies can enter.

As a result, they point to the technological ones listed above Areas of commonly used primed or unprimed substrates, which are coated with at least one coating according to the invention, with bonded and / or with at least one adhesive layer according to the invention are sealed at least one seal according to the invention, in one a particularly advantageous application-related property profile particularly long service life based on what makes them economical and ecological makes it particularly attractive.

Examples Production Example 1 The production of a methacrylate copolymer (A)

In a suitable reactor, equipped with a stirrer, two dropping funnels for the monomer mixture and the initiator solution, nitrogen inlet tube, Thermometer, heater and reflux condenser, 650 parts by weight was one Aromatic hydrocarbon fraction with a boiling range of 158 to Weighed in 172 ° C. The solvent was heated to 140 ° C. After that were a monomer mixture of 652 parts by weight of ethylhexyl acrylate, 383 Parts by weight of 2-hydroxyethyl methacrylate, 143 parts by weight of styrene, 212 Parts by weight of 4-hydroxybutyl acrylate and 21 parts by weight of acrylic acid within of four hours and an initiator solution from 113 parts by weight of the aromatic solvent and 113 parts by weight of tert-butyl perethylhexanoate evenly metered into the template within 4.5 hours. With the dosage the monomer mixture and the initiator solution were started simultaneously. To the resultant reaction mixture became the termination of the initiator feed heated to 140 ° C with stirring for a further two hours and then cooled. The resulting solution of the methacrylate copolymer (A) was mixed with a mixture of 1-methoxypropylacetate-2, butylglycol acetate and butyl acetate diluted. The resulting solution had a solids content of 65% by weight, determined in a convection oven (one hour / 130 ° C), and an acid number of 15 mg KOH / g solids.

example 1 The production of a clear lacquer according to the invention

The clearcoat material of the invention was prepared by mixing the constituents listed in the table in the order given and homogenizing the resulting mixture. The material composition of the clear lacquer according to the invention component parts by weight Master batch: Methacrylate copolymer of preparation example 1 35,90 dipentaerythritol 20.00 UV absorber (substituted hydroxyphenyltriazine) 1.00 HALS (N-methyl-2,2,6,6-tetramethylpiperidinyl ester) 1.00 Wetting agent (Byk® 306 from Byk Chemie) 0.40 butyl 27,40 Solventnaphtha® 10,80 Irgacure® 184 (commercial photoinitiator from Ciba Specialty Chemicals) 2.00 Genocure® MBF (commercial photoinitiator from Rahn) 1.00 Lucirin® TPO (commercial photoinitiator from BASF AG) 0.50 Total: 100.00 Crosslinking agent component 1B): Total: 38.28 Crosslinking agent (B1): Isocyanatoacrylat Roskydal ® UA VPLS 2337 from Bayer AG (basis: trimeres hexamethylene diisocyanate; content of isocyanate groups: 12% by weight) 27.84 Crosslinking agent (B2): Isocyanatoacrylate based on the trimer of isophorone diisocyanate (70.5% in butyl acetate; viscosity: 1,500 mPas; content of isocyanate groups: 6.7% by weight; produced as in Example 1 of EP 0 928 800 A1) 6.96 thinner 3.48

The clear lacquer according to the invention had a very good pot life and a very good one Application behavior.

Example 2 The production of a coloring according to the invention Multi-layer coating

To produce the multi-layer coating system according to the invention, steel panels were coated in succession with a cathodic electrodeposition coating which had been baked at 170 ° C. for 20 minutes and had a dry layer thickness of 18 to 22 μm. The steel sheets were then coated with a commercially available two-component water filler from BASF Coatings AG, as is usually used for plastic substrates. The resulting filler layer was baked at 90 ° C. for 30 minutes, so that a dry layer thickness of 35 to 40 μm resulted. A commercial black waterborne basecoat from BASF Coatings AG with a layer thickness of 12 to 15 μm was then applied, after which the resulting waterborne basecoat films were flashed off at 80 ° C. for ten minutes. The clearcoat material of Example 1 according to the invention was then pneumatically applied with a layer thickness of 40 to 45 μm in a cloister with a flow cup gun. The water-based lacquer layers and the clear lacquer layers were cured for 5 minutes at room temperature, for 10 minutes at 80 ° C., followed by exposure to UV light at a dose of 1,500 mJ / cm ² , and finally for 20 minutes at 140 ° C.

The multicoat paint system of the invention was excellent Property profile on.

The multi-layer coating was very brilliant and had a gloss (20 °) according to DIN 67530 from 90.5. The micro penetration hardness (universal hardness at 25.6 mN, Fischerscope 100 V with diamond pyramid according to Vickers) was 138.1.

The scratch resistance was determined using the sand test (cf. the German Patent application DE 139 39 453 A1, page 9, lines 1 to 63) using the Test plates described above assessed. There were after damage only a loss of gloss by 10 units (20 °) to 80.5 determined what the high scratch resistance underpinned.

In addition, the scratch resistance was checked using the brush test (see German Patent application DE 198 39 453 A1, page 9, lines 17 to 63) using the Test plates described above assessed. There were after damage only a loss of gloss by 4 units (20 °) to 86.5 was determined, which is the high Scratch resistance underpinned.

The MB gradient oven test known in the technical field showed the first Damage to the clear coat by sulfuric acid only from one Temperature of 53 ° C and tree resin only from 55 ° Celsius. The etch Persistence was excellent.

Claims (18)

1. Containing coating materials curable thermally and with actinic radiation A) at least one binder with isocyanate-reactive functional groups and B) containing a crosslinking agent component a) free and / or blocked isocyanate groups, b) reactive functional groups containing at least one bond which can be activated with actinic radiation, c) flexibilizing segments which, as a component of three-dimensional networks, lower their glass transition temperature Tg, and d) hardening segments which, as a component of three-dimensional networks, increase their glass transition temperature Tg; with the proviso that the crosslinking agent component (B) contains or consists of at least one component which has the features (i) and (ii). 2. Coating materials according to claim 1, characterized in that the Crosslinking agent component (B) at least two components, both have, contains or consists of features (i) and (ii). 3. Coating materials according to claim 2, characterized in that the crosslinking agent component (B) 1. at least one component contained in the molecule on a statistical average a) at least one free and / or at least one blocked isocyanate group, b) at least one reactive functional group with at least one bond which can be activated with actinic radiation and c) at least one flexibilizing segment which lowers the glass transition temperature Tg as a component of three-dimensional networks; and 2. at least one component containing the molecule in the statistical average a) at least one free and / or at least one blocked isocyanate group, b) at least one reactive functional group with at least one bond which can be activated with actinic radiation and c) at least one hardening segment, which increases the glass transition temperature Tg as a component of three-dimensional networks; contains or consists of. 4. Coating materials according to claim 2 or 3, characterized in that the crosslinking agent component (B) contains or consists of at least one constituent which can be produced by the one- or multi-stage reaction 1. a mixture of 1. at least one polyisocyanate containing, on average, at least two free isocyanate groups in the molecule, or at least two free isocyanate groups and at least one blocked isocyanate group and at least one flexibilizing segment which, as a component of three-dimensional networks, lowers their glass transition temperature Tg; and 2. at least one polyisocyanate containing, on average, at least two free isocyanate groups in the molecule, or at least two free isocyanate groups and at least one blocked isocyanate group, and at least one hardening segment which, as a component of three-dimensional networks, increases their glass transition temperature Tg; With 2. at least one compound containing, in the molecule, at least one isocyanate-reactive functional group and at least one reactive functional group with at least one bond which can be activated with actinic radiation. 5. Coating materials according to claim 1, characterized in that the crosslinking agent component (B) at least one component which can be produced by the reaction in the first stage of 1. at least one polyisocyanate containing, on average, at least two free isocyanate groups in the molecule, or at least two free isocyanate groups and at least one blocked isocyanate group and at least one flexibilizing segment which, as a component of three-dimensional networks, lowers their glass transition temperature Tg; With 2. at least one compound with at least two isocyanate-reactive functional groups and at least one hardening segment, which as a component of three-dimensional networks increases their glass transition temperature Tg, in the molecule, or alternatively by implementing it in the first stage of 1. at least one polyisocyanate containing, on average, at least two free isocyanate groups in the molecule, or at least two free isocyanate groups and at least one blocked isocyanate group, and at least one hardening segment which increases the glass transition temperature Tg as a component of three-dimensional networks; With 2. at least one compound with at least two isocyanate-reactive functional groups and at least one flexibilizing segment, which as a component of three-dimensional networks lowers their glass transition temperature Tg, in the molecule, or alternatively by implementing the first level of
1.1) with [1.3) + 1.4)],
1.2) with [1.4) + 1.3)],
[1.1) + 1.2)] with 1.3),
[1.1) + 1.2)] with 1.4) and
[1.1) + 1.2)] with [1.3) + 1.4)];
in an equivalent ratio that the resulting precursors 3.) contain on average at least two free isocyanate groups, or at least two free isocyanate groups and at least one blocked isocyanate group in the molecule;
and by implementing the preliminary stage 3.) in a further stage 1. at least one compound containing, on average, at least one isocyanate-reactive functional group and at least one reactive functional group with at least one bond which can be activated with actinic radiation; contains or consists of. 6. Coating materials according to one of claims 1 to 5, characterized characterized in that the binder (A) from the group consisting of statistical, alternating and block-like, linear, branched and comb-like, thermal and thermal and with actinic Radiation-curable polyaddition resins and polycondensation resins and (co) polymers of olefinically unsaturated monomers, to be selected. 7. Coating materials according to one of claims 1 to 6, characterized characterized in that the isocyanate-reactive groups from the group, consisting of hydroxyl, thiol and primary and secondary Amino groups. 8. Coating materials according to claim 7, characterized in that the isocyanate-reactive groups are hydroxyl groups. 9. Coating materials according to one of claims 1 to 8, characterized characterized in that the binder (A) still on average at least one reactive functional group with at least one contain actinic radiation activatable bond in the molecule. 10. Coating materials according to one of claims 1 to 9, characterized characterized in that the bonds which can be activated with actinic radiation from the group consisting of carbon-hydrogen single bonds or carbon-carbon, carbon-oxygen, carbon Nitrogen, carbon-phosphorus or carbon-silicon Single bonds or double bonds can be selected. 11. Coating materials according to claim 10, characterized in that the Bonds that can be activated with actinic radiation Double bonds ("double bonds") are. 12. Coating materials according to one of claims 1 to 11, characterized characterized in that the flexibilizing segments from the group, consisting of double-bonded aliphatic hydrocarbon residues and divalent aliphatic containing heteroatoms Hydrocarbon residues can be selected. 13. Coating materials according to claim 12, characterized in that the flexibilizing segments are hexamethylene residues. 14. Coating materials according to one of claims 1 to 13, characterized characterized in that the hardening segments from the group, consisting of aromatic and double-bonded and cycloaliphatic radicals. 15. Coating materials according to claim 14, characterized in that the Cycloaliphatic residues are isophorone residues. 16. Use of the coating materials according to one of claims 1 to 15 for the production of single and multi-layer clear coats, as well as single and multilayer, color and / or effect, electrically conductive, magnetically shielding and / or fluorescent coatings. 17. Use of the coating materials according to one of claims 1 to 15 as adhesives and sealants. 18. Use according to claim 16 or 17, characterized in that the Coating materials, adhesives or sealants for painting, Bonding and sealing of motor vehicle bodies and parts thereof, Motor vehicles indoors and outdoors, buildings indoors and Exterior, doors, windows and furniture as well as for painting, Bonding and sealing as part of the industrial painting of Small parts, coils, containers, packaging, electrotechnical components and white goods can be used.